Chemical process



Patented Sept. 10, 1946 ED; sTATl=..S

CHEMICAL PROCESS Charles WatRinSQCranford', .,.a ssignor to Standard OilDevelopment Company, acorva199. .9.?! 9? ela ar No Drawing. ApplicationApr-1117,1943, g i SerialNo.483,'498 -W' The presentinvention relates toimprovements in the art of alkylating propylene'with isobutane;employing aluminum chloride-hydrocarbon com: plex catalyst.

., The alkylation of propylenelwith isobutanein 5 thepresence of strongsulfuric acid, sayover90 acid concentration. has, not provedsatisfactory becauseof excessive acid consumption.-

I have discovered a method of alkylatin nropyle ewith 'is bu ne. and theist of t eme ti n res des n mpl x n alum numich c idee ydrqqa bo 12 9Xcata yst, w ich; Lhe iound tqp ssess lon a l s li e and; oilet .qe ab cpfprbd c ne o d. yields o a kyla 19 hi h quality- .1; ,5: .1 i; I The maaobl 9 m -i v t 9n,. h 9 ore. i o s nthes eh dro a bon bo li n the ease-1ine,rang .,of 2 9 antiet n t v qu lit in good yield rom nr n and i ute. x 2 2 91 I 21 he u et lwi h-tqpoi t outthatlha discovered that acertainaluminum chloride-hydrocarbon complex formed by contactingisobutane, propylene and aluminum chlorideprovides anactivecatalystforthe allrylation o'i propylene withisobutane which Ihave also found remains active oyerj n extended period of time. 'I have76 6 9 m... new I further found that a small amount ofia volatilehalide, suchlas ethyl chloride, hydrogen chloride, ortmethyl chloride,when added to thereaction mass; improves the performance of catalyst andisotherwise desirable.

1 Since the preparation of the catalyst is an important featureofmy;inventi0n, I shall now de-' scribe in detail theimethod of preparingthe same. I charged lb. of A1013. to a turbo mixer and then added 69gram niolsof liquefied isobutane containing 51% by volume of ethylchloride. The mixturewas thoroughly agitated. At 70 F., 23 .gram mole ofpropylene were addedover a period of 2 hours and 18 minutes whilestirring. The stirring was continued for A. of an hour following theaddition of the olefin. The pressure averaged-1'10 lbs./sq.-in. duringthe operation. The mixture was permitted to remain quiescent to allowstratification and'settling of the material into a lower brown, mobileliquid layer; containing an Al'Cla hydrocarbon complex and an upperproduct layer (i. e. analkyl'ate, formed by reactingpropylene withisobutane). I repeated the operation as previously outlined 26 times.except 25 tha' no additional A1013 was-added until the 25th run and asotherwiseindicated in the below Table I;

V 7 I "TABLEIVVV RrbpyZen'e-kobuiane alkylaiion+3 gallon turbo midrcf-liqi h op raiiqHa z/ 22? grams f AZCL: as a hydrocarbon complex-promote.ethyl chloride 2 Run No'IEA7-g', x

Reactiontemp.,F;. 71 71 72 70 70 72, 70 71 69 70 50W'49'; 70 .40 91 '69.90 70 71 70 70 71 70*1507272 EtQl vol.% on C v 5 1.0 0.5 0.2 0.5 ,0.20.2 Tr. 0.2 0.2 5 0.50.5 50.505 Isocharged, gram mols. 69.-- 39 40 3960... 39 Prop lene charged, gram 1 1 mo s..'-2Z 23 13 p s 13 20 1s-Isobutane/ptopylene mol -ratio 3 3 4 5 3 Propylene addition ra "i'gtammols ......L.' 8 10 l0 10 10 13 8 10 10 10 10" 10 9 10 10 9 3 9 10 10 1O8 8 8 8 Totalalkylata yield,W l ;v

%'(based on olefln)-. 229 241252254 250 239 218 224 226 234 ,229212 240214 225191 215212211 152 156220183 -1roductdlstribution: f i w 1 1 a 9.60.1l0. Facut (C|), .vol.-' .1 j, 1 y 6715 141618 2168 2 2 1 0 0 0,2 2000200 21 12 1913 1916 1816.18.10 .4 s;q--2- '310 3 a 2 2 1 1 4 9 5 4 2-165210F.cut(C1),vol. 1 I 47 4138 39 35 30 31 56 r 77 71 70 75 60 69 66-71 57 60 45 43 25 31 60 210-265F.-c H01), vol. i

'11 12 11 99 9 9 9 9 9 12 12 1 1119 ,13 11 14} is 1413 14} 1a 1o 13 17l1 l0 l0 9 9 v 9 8 5 8 ll 7 '14 12 '17 9 27 23 32 36 41 26 32 ,LS. .M.ct.No. '(60-266" F; cut) 84.2 82. 82.1 83.3 85.5 84.5 84.2 "186.3 86.3.-- 89.5

BromlneNo.(60-266F.cut). Nil Nil Nil Nil N11l l p. s. i. H. imposed onreactor.

-| 25 31115.0! A1011 dded w reactor in addition to the zzi'g s.originally.

' 10 :ms. of A101; added to reactor in addition to tho227 amsioriglnallyIn the foregoing runs, it will be noted from the table that during thefirst seven runs the'amount figure was verified in other runs. Also, thetemperature was varied up to 150 F. (Run 24) but the data indicates thatbest resultsare'obtainable 'i A1013. Subsequent test runs, usingabout5.1%.

AlCl3 by weight present as hydrocarboncompl'ex based ontotalhydrocarbons, gave-best results. Table II below shows this in sixruns:-

-TABLE II Propylene-,isobut ne aZIcyZation-AZCZ3-hydro cgrhon complexcatalyst reaction temperature,

7 70 F.,-batch operation [Efiect of catalyst/hydrocarbon weight ratio]Wt. %'AIC13 Total alkylate yield, wt. (based on olefin :1v 180-149 242265 Product distributin,vo1.%:

60- 0? F.cut 0 l 7 37 2 10 21 25' 61 20 3 g 11 6 63' 11 1 A1013 presentas a hydrocarbon complex. Percentage based'on total hydrocarbons.

The above runs show that 0.5% AlC la produce a virtually inactivecatalyst; while 20% is an; amount causing the formation oftoo great 2.Further, runs showed quantity of light ends. that from 3 to 7% A1013gave goodresults.

My process may be operated" continuously; and" the' best procedure is toflow the isobutane andpropylene feeds through a vessel orreceptaclecontaining the A1613. Foripor 5 hours, when=the process isstarted, the AlCls-hydrocarbon co'mplex is formed and after thatinduction period, the process isoperated'to maintain the optimumconditions indicated in the preceding tables.

and the catalyst for a period of from about /3 hour to 1%, hours., Also,while the isobutane should be in excess over the propylene in the re.-action mass, the mo] ratio of isobutane to propylene may vary from 2 to10. mols of. isobutane per mol of propylene, The best temperature rangein the reaction zone is from about 70 to' 90 although temperatures from50 to 150may be used, and the preferred pressure range therein is from'75 to 250 lbs/sq. in. gauge. With respect to the activation, HCl may beused. in amounts from 0.001 to 5% based on the isobutane. From 0.1 to10% ethyl chloride or methyl chloride may be used for a like purpose.

Numerous modifications of my invention falling within the spirit thereofmay be made by,-

those familiar with this art.

As to contact times, good, results are achieved bypermittingthereactants to contact each other I claim: I 1. Process of alkylatingpropylene with isobutane which comprises contacting the propylene withan excess of isobutane in the presence of a liquid aluminumchloride-hydrocarbon complex as the alkylating catalyst formed bycontacting for an extended period of time aluminum chloride withisobi-itane and propylene.

2-, The-.met hod -set forth in claim 1 in which the alkylation processis carried out at a temperaturejwithin the range of about 50-150 F.

. The process set forth in claim 1, in which a promoteris used which isone of the class consisting of alkyl halides and HCl.

4. The process set forth in claim 1 in which from 0.001' 5-%by-weight-ofhydrogen chloride based on the isobutane is employed asapromoter.

5. The process set forth in claim liinwhich from 0.01- to 10% by weightof ethyl chloride-based on the isobutane is-employed as a promoter.

6. Theprocess of claim 1 in whicli-fr'om 0 .01 to 10% by weight-ofmethyl chloridebasedon the isobutane is employed as a promoter.

'7. The method-set-forth in claim 1 m which the liquid-aluminumchloride-hydrocarbon complex catalyst is prepared insituunder' reacti'onconditions using the olefin and isoparaffin which are to be alkylated incontacting relationship with the aluminum chloride. e

8: The method'of -claim 1 performed-in" the presence of from 0.2 to 0.5%ethyl chloridebased on the isobutane, a-t-temperatures oflfrom'70 to 90R, under superatmo'spheric pressure: and during contact times of from /2to 1% hours.

9. The-method of claim 1 in which thepre sure ranges from 75120250 lbs./sq';i n-.'

10. The method of claim 1 performed con tinuously by adding AlCl; to thereactants so as to maintain an A1013 hydrocarbon complex to totalhydrocarbons; weight percentage of about 5, adding the reactantscontinuously and'withdraw ing product continuously.

11. In the process of, alkylating an olefin with an excess: ofisoparaffin in the presence of an aluminum chloride-hydrocarbon complexcatalyst the improvement which comprises contacting aluminum chloridewith isobutane and propylene for a period of" time sufficient to form aliquid aluminum chloride-hydrocarbon complex catalyst and contactingpropylene'with an'excess of'isobutane in the, presence of said catalyst;

12. In the process of alkylating anolefinwith an excess of anisoparaffin in the presence ofyan aluminum chloride-hydrocarbon complexcatalyst the improvement which comprisesmixing aluminum chloride withliquefied isobutane; agitating the mixture until thetemperaturereaches Iabout R, admixing propylene to themixture; agitat- 7 ing the mixture fora timesuific'ientjtoconvert the aluminum chloride into aliquid' aluminumchloride-hydrocarbon complex, allowing. the ,mixture to stratify andcontacting the lower.- liquid; layer comprising said liquid.aluminum.chloride hydrocarbon complex withadditional'arnountspf,propylene and excessisobutane. 1 7

13. The process set forth in claim;1,2.-,-in.whlch an excess ofisob-utane based on the pnopylene addedismixed with the aluminum.chloride.

the class consisting, of alkylihalides'a-nd hydljQgen chloride, v. H

hydrocarbon complex catalyst.

16. The process set forth in claim 11 in which isobutane and propyleneare contacted with aluminum chloride for about 4-5 hours to form saidliquid aluminum chloride-hydrocarbon complex c present in the form of aliquid aluminum chloride 5 catalyst.

CHARLES H. WATKINS.

